阅读说明：本技术 一种耐高温交联剂及超高强度的绝缘材料 (High-temperature-resistant cross-linking agent and ultrahigh-strength insulating material ) 是由 林伟男 李天林 于 2019-12-19 设计创作，主要内容包括：本发明了一种可耐高温且有超高强度的乙烯-四氟乙烯共聚物的绝缘材料,所述超高性能交联乙烯-四氟乙烯共聚物材料由如下原料：乙烯-四氟乙烯共聚物(ETFE)、耐高温敏化剂、Sb<Sub>2</Sub>O<Sub>3</Sub>、Sb<Sub>2</Sub>O<Sub>5</Sub>、四[β-(3,5-二叔丁基-4-羟基苯基)丙酰]季戊四醇酯、二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯、乙撑双硬脂酰胺、白油。本发明了具有耐高温的敏化剂,解决了目前市场上交联剂所存在的易自聚、易分解、交联度低等问题,不仅大大提高了XETFE的力学性能,而且也提高了XETFE的耐热性能和耐辐射性能。(The invention discloses an insulating material of an ethylene-tetrafluoroethylene copolymer with high temperature resistance and ultrahigh strength, which is prepared from the following raw materials: ethylene-tetrafluoroethylene copolymer (ETFE), high-temperature sensitizer and Sb 2 O 3 、Sb 2 O 5 Tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl]Pentaerythritol ester, diethylene glycol bis [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl)) Propionate, ethylene bis stearamide, white oil. The high-temperature-resistant sensitizer solves the problems of easy self-polymerization, easy decomposition, low crosslinking degree and the like of the crosslinking agent in the current market, greatly improves the mechanical property of the XETFE, and also improves the heat resistance and the radiation resistance of the XETFE.)

1. A high-temperature resistant crosslinking agent is characterized by having the following chemical structural formula:

wherein R is selected from one of olefin, benzene ring, naphthalene ring and biphenyl.

2. The high temperature crosslinking agent of claim 1, wherein the high temperature crosslinking agent is selected from the group consisting of

3. The high-temperature crosslinking agent of claim 1, wherein the high-temperature crosslinking agent has a self-polymerization temperature of 350 ℃ to 400 ℃.

4. The high-temperature-resistant crosslinking agent as claimed in claim 1, wherein the number average molecular weight of the high-temperature-resistant crosslinking agent is preferably 500 to 1500.

5. An insulation material of ethylene-tetrafluoroethylene copolymer containing the high temperature resistant crosslinking agent according to any one of claims 1 to 4, wherein the insulation material comprises the following components in parts by weight:

100 parts of ethylene-tetrafluoroethylene copolymer material;

1-5 parts of the high-temperature-resistant crosslinking agent as defined in claim 1;

Sb₂O₃3-6 parts;

Sb₂O₅1-3 parts;

0.1-1 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] pentaerythritol ester;

0.1-1 part of diethylene glycol bis [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate;

0.1-1 part of ethylene bis stearamide;

0.1-1 part of white oil.

6. A process for producing an ethylene-tetrafluoroethylene copolymer insulating material according to claim 5, which comprises the steps of:

(1) mixing ethylene-tetrafluoroethylene copolymer material, high temperature resistant cross-linking agent and Sb₂O₃、Sb₂O₅Tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl]Adding pentaerythritol ester, diethylene glycol bis [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, ethylene bis stearamide and white oil into a high-speed mixer according to the above proportion, and uniformly mixing for 20 min;

(2) extruding and granulating the mixed raw materials through a double-screw extruder to obtain granules, and drying the mixed granules in a (30-60) DEG C drying oven for 18-36 h;

(3) pressing the dried granules into square sheets with the thickness of 2mm by a hot press; then irradiating under electron radiation; after irradiation, the samples were placed at 150 ℃ for 2h for post-treatment and finally taken out.

7. The method as claimed in claim 6, wherein in the step (2), the temperatures of the sections of the twin-screw extruder are (190-; the head temperature was 270 ℃.

8. The method as claimed in claim 6, wherein in the step (2), the temperatures of the sections of the twin-screw extruder are respectively 200 ℃, 260 ℃, 265 ℃, 270 ℃; the head temperature was 270 ℃.

9. The method according to claim 6, wherein in the step (3), the irradiation dose of the irradiation is 10-15 Mrad.

10. The high-temperature crosslinking agent of claim 1, wherein the decomposition temperature of the high-temperature crosslinking agent is 450 to 500 ℃.

Technical Field

The invention relates to an insulating material, in particular to a high-temperature-resistant cross-linking agent and an ultrahigh-strength insulating material

Background

The crosslinked ethylene-tetrafluoroethylene (XETFE) insulated wire and cable has the excellent performances of high temperature resistance level, good mechanical property, aging resistance, chemical solvent resistance and the like, and has the characteristics of small volume, light weight and the like, and is mainly applied to various special occasions with high reliability requirements, small installation space and light weight requirements, and is increasingly widely applied to aerospace in particular. But the domestic market is totally dependent on import for a long time and is expensive. With the technical progress and the progress of localization, the XETFE insulated wires and cables produced by domestic enterprises have gradually entered the aviation field in recent years. The key and technical difficulty of the formulation of the XETFE insulating material lies in finding a proper sensitizer. The existing sensitizers sold in the market or disclosed in the patent are not perfect in comprehensively solving the problems of self-polymerization, thermal stability, high-temperature volatilization and the like. Therefore, the synthesis or search for a suitable ETFE radiation sensitizer is the key to the development of XETFE insulators.

Disclosure of Invention

The invention provides a high-temperature-resistant crosslinking agent, which has the following chemical structural formula:

wherein R is selected from one of olefin, benzene ring, naphthalene ring and biphenyl.

As an embodiment of the invention, the high temperature resistant cross-linking agent is selected from

One of (1); wherein n is 1-10.

In one embodiment of the present invention, the self-polymerization temperature of the high temperature resistant crosslinking agent is 350 to 400 ℃.

In one embodiment of the present invention, the number average molecular weight of the high temperature resistant crosslinking agent is preferably 500 to 1500.

The second aspect of the present invention provides an insulating material containing the ethylene-tetrafluoroethylene copolymer containing the high temperature resistant crosslinking agent, which comprises the following components in parts by weight:

a third aspect of the present invention provides a method for producing the above-mentioned insulating material of ethylene-tetrafluoroethylene copolymer, comprising the steps of:

(1) mixing ethylene-tetrafluoroethylene copolymer material, high temperature resistant cross-linking agent and Sb₂O₃、Sb₂O₅Tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl]Adding pentaerythritol ester, diethylene glycol bis [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, ethylene bis stearamide and white oil into a high-speed mixer according to the above proportion, and uniformly mixing for 20 min;

(2) extruding and granulating the mixed raw materials through a double-screw extruder to obtain granules, and drying the mixed granules in a (30-60) DEG C drying oven for 18-36 h;

(3) pressing the dried granules into square sheets with the thickness of 2mm by a hot press; then irradiating under electron radiation; after irradiation, the samples were placed at 150 ℃ for 2h for post-treatment and finally taken out.

As an embodiment of the invention, in the step (2), the temperatures of the sections of the twin-screw extruder are (190-; the head temperature was 270 ℃.

In one embodiment of the invention, in the step (2), the temperatures of the sections of the twin-screw extruder are respectively 200 ℃, 260 ℃, 265 ℃, 270 ℃ and 270 ℃; the head temperature was 270 ℃.

In one embodiment of the present invention, in the step (3), the irradiation dose of the irradiation is 10 to 15 Mrad.

In one embodiment of the present invention, the decomposition temperature of the high temperature resistant crosslinking agent is 450 to 500 ℃.

Has the advantages that:

1. the high-temperature resistant sensitizer comprehensively solves the problems of self-polymerization, thermal stability, high-temperature volatilization and the like of the existing commercially available or patented sensitizer, and compared with the existing sensitizers TAC and TAIC in the market, the self-polymerization temperature is as high as 350-400 ℃, and the decomposition temperature is 450-500 ℃.

2. The high-temperature-resistant sensitizer comprehensively solves the problems of high smoke generation, easy decomposition of the sensitizer, easy yellowing of materials, unstable product performance and the like in the conventional ETFE processing process; the product is extruded into white transparent state and does not change color after being irradiated. Compared with the sensitizing agents TAC and TAIC on the market, the smoke generation amount in the extrusion processing is larger, the sensitizing agents are decomposed in a large amount, the crosslinking effect is lost, the product is yellow, the color is deepened after irradiation, and the obvious effect is achieved.

Detailed Description

For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

Moreover, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.

The invention provides a high-temperature-resistant crosslinking agent, which has the following chemical structural formula:

wherein R is selected from one of olefin, benzene ring, naphthalene ring and biphenyl.

As an embodiment of the invention, the high temperature resistant cross-linking agent is selected from

One of (1); wherein n is 1-10.

In one embodiment of the present invention, the self-polymerization temperature of the high temperature resistant crosslinking agent is 350 to 400 ℃.

In one embodiment of the present invention, the number average molecular weight of the high temperature resistant crosslinking agent is preferably 500 to 1500.

The second aspect of the present invention provides an insulating material containing the ethylene-tetrafluoroethylene copolymer containing the high temperature resistant crosslinking agent, which comprises the following components in parts by weight:

a third aspect of the present invention provides a method for producing the above-mentioned insulating material of ethylene-tetrafluoroethylene copolymer, comprising the steps of:

(1) mixing ethylene-tetrafluoroethylene copolymer material, high temperature resistant cross-linking agent and Sb₂O₃、Sb₂O₅Tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl]Adding pentaerythritol ester, diethylene glycol bis [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, ethylene bis stearamide and white oil into a high-speed mixer according to the above proportion, and uniformly mixing for 20 min;

(2) extruding and granulating the mixed raw materials through a double-screw extruder to obtain granules, and drying the mixed granules in a (30-60) DEG C drying oven for 18-36 h;

(3) pressing the dried granules into square sheets with the thickness of 2mm by a hot press; then irradiating under electron radiation; after irradiation, the samples were placed at 150 ℃ for 2h for post-treatment and finally taken out.

As an embodiment of the invention, in the step (2), the temperatures of the sections of the twin-screw extruder are (190-; the head temperature was 270 ℃.

In one embodiment of the invention, in the step (2), the temperatures of the sections of the twin-screw extruder are respectively 200 ℃, 260 ℃, 265 ℃, 270 ℃ and 270 ℃; the head temperature was 270 ℃.

In one embodiment of the present invention, in the step (3), the irradiation dose of the irradiation is 10 to 15 Mrad.

In one embodiment of the present invention, the decomposition temperature of the high temperature resistant crosslinking agent is 450 to 500 ℃.

The following is a detailed description of specific embodiments.